SBA-15负载的N-杂环卡宾-吡啶钼配合物在二氧化碳转化制备环状碳酸酯中的应用

doi:10.6023/cjoc202405037

摘要/Abstract

由二氧化碳(CO₂)和环氧化物合成环状碳酸酯是CO₂利用的有效途径. 尽管各类金属催化剂相继见诸报道, 但依然急需开发一类可回收或再循环的催化剂. 该工作将SBA-15负载的N-杂环卡宾-吡啶钼络合物(Mo@SBA-15)作为一类高效和可循环利用的催化剂应用于CO₂和环氧化物合成环状碳酸酯. Mo@SBA-15与四丁基溴化铵(TBAB)组成的双组分催化体系在100 ℃和CO₂ (1 MPa)压力下合成环状碳酸酯时, 显示出了较高的催化活性. 此外, Mo@SBA-15重复使用7次未发现明显的活性降低.

关键词: 二氧化碳, 环状碳酸酯, 钼催化剂, CO₂利用, 非均相催化剂

Synthesis of cyclic carbonates from carbon dioxide (CO₂) and epoxides is an effective pathway for the CO₂ utilization. Although various metal catalysts have been reported, it is highly desirable to develop a method for the reuse or recycling of catalysts. Herein, an N-heterocyclic carbene-pyridine molybdenum complex supported over SBA-15 (Mo@SBA- 15) was used as an efficient and recyclable catalyst for converting CO₂ and epoxides into cyclic carbonates. Mo@SBA-15 in combination with tetra-butylammonium bromide (TBAB) shows high catalytic activity in the synthesis of cyclic carbonates under 100 ℃ and 1 MPa CO₂ pressure. In addition, Mo@SBA-15 was reused seven times without any significant activity loss.

Key words: carbon dioxide, cyclic carbonate, molybdenum catalyst, CO₂ utilization, heterogeneous catalyst

引用此文

李建文, 王涛, 陶晟, 陈飞, 李敏, 刘宁. SBA-15负载的N-杂环卡宾-吡啶钼配合物在二氧化碳转化制备环状碳酸酯中的应用[J]. 有机化学, 2024, 44(10): 3213-3222.

Jianwen Li, Tao Wang, Sheng Tao, Fei Chen, Min Li, Ning Liu. N-Heterocyclic Carbene-Pyridine Molybdenum Complex Supported over SBA-15 for Converting of Carbon Dioxide into Cyclic Carbonates[J]. Chinese Journal of Organic Chemistry, 2024, 44(10): 3213-3222.

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图/表 17

Figure 1. Structure of Mo@SBA-15

Figure 2. Fourier-transform infrared spectroscopy spectra of fresh (a) 1a, (b) SBA-15, and (c) Mo@SBA-15

Figure 3. Low-angle X-ray diffraction patterns of (a) SBA-15 and (b) Mo@SBA-15

Figure 4. SEM images of (a) SBA-15 and (b) Mo@SBA-15; TEM images of (c, e) SBA-15 and (d, f) Mo@SBA-15; (g) EDS-mapping of Mo@SBA-15

Figure 5. (a) Nitrogen adsorption-desorption isotherms and (b) pore size distribution of SBA-15 and Mo@SBA-15

Figure 6. XPS survey spectra of Mo@SBA-15

Entry	Catalyst	C	N	H
1	SBA-15	0.46	—	1.52
2	Mo@SBA-15	7.79	1.01	0.954

Table 1. Elemental analysis of the catalyst

Figure 7. TGA curves of SBA-15 and Mo@SBA-15

Entry	Catalyst (mg)	Cocatalyst (mol%)	T/℃	p/MPa	Time/h	Yield/%
1	None	None	100	1	6	0
2	Mo@SBA-15 (50)	TBAB (3)	100	1	6	97
3	None	TBAB (3)	100	1	6	62
4	Mo@SBA-15 (50)	None	100	1	6	0
5	Mo complex 1a (50)	TBAB (3)	100	1	6	94
6	(3-Chloropropyl) trimethoxysilane (50)	TBAB (3)	100	1	6	46
7	SBA-15 (50)	TBAB (3)	100	1	6	71
8	Mo@SBA-15 (50)	TBAB (3)	30	1	6	27
9	Mo@SBA-15 (50)	TBAB (3)	60	1	6	52
10	Mo@SBA-15 (50)	TBAB (3)	80	1	6	73
11	Mo@SBA-15 (50)	TBAB (3)	100	0.5	6	70
12	Mo@SBA-15 (50)	TBAB (3)	100	1.5	6	88
13	Mo@SBA-15 (20)	TBAB (3)	100	1	6	87
14	Mo@SBA-15 (30)	TBAB (3)	100	1	6	94
15	Mo@SBA-15 (40)	TBAB (3)	100	1	6	96
16	Mo@SBA-15 (30)	TBAB (1)	100	1	6	49
17	Mo@SBA-15 (30)	TBAB (2)	100	1	6	82
18	Mo@SBA-15 (30)	TBAB (3)	100	1	2	71
19	Mo@SBA-15 (30)	TBAB (3)	100	1	4	82
20	Mo@SBA-15 (30)	TBAB (3)	100	1	10	97

Table 2. Optimization of the synthesis of 4-ethyl-1,3-dioxolan-2-onea

Table 3. Scope of the substratesa

Scheme 1. Proposed mechanism for the molybdenum-catalyzed cycloaddition of CO2

Figure 8. (a) Recycling of the molybdenum catalyst; (b) recycling experiments under the following reaction conditions: EB (10 mmol), Mo@SBA-15 (30 mg), CO2 (1 MPa), TBAB (96.6 mg, 0.3 mmol), no solvent, 100 ℃, 6 h

Figure 9. FT-IR spectra comparison of (a) fresh Mo@SBA-15 and (b) reused Mo@SBA-15 after being recycled seven times

Figure 10. (a) Mo@SBA-15 SEM image of recycled catalyst; (b, c) Mo@SBA-15 TEM image of recycled catalyst

Figure 11. Low-angle X-ray diffraction patterns of (a) reused Mo@SBA-15 after being recycled seven times and (b) fresh Mo@SBA-15

Entry	Cat.	Nucleophile (mol%)	Epoxide	T/℃	Time/h	p/MPa	Yield/%	Runs
1^[51]	MoCl₅ (0.5 mol%)	PPh₃(3)	PO	r.t.	168	0.1	79.0	0
2^[52]	MoO₃ (2 mol%)	[Bu₄P]Br (2)	EMO	100	16	5	98.0	0
3^[53]	Mo catal. (1 mol%)	TBAB (7.2)	PO	25	24	0.1	97.5	0
4^[54]	Mo catal. (0.1 mol%)	Neat	ECH	100	3.5	1	56.3	0
5^[55]	Mo catal. (0.5 mol%)	TBAI (2)	EB	30	24	0.5	94.0	0
6^[56]	Mo catal. (0.15 mol%)	TBAB (5)	ECH	70	3	0.1	99.9^b	5
7^[57]	Mo catal. (0.1 mmol)	TBAB (1)	SO	50	48	0.5	99.0^b	3
8^[49]	Mo catal. (0.5 mol%)	TBAI (2)	EB	80	20	0.5	91.0	0
9 (our work)	Mo@SBA-15 (30 mg)	TBAB (3)	EB	100	6	1	94.0^b	7

Table 4. Comparison of molybdenum based catalysts in carbon dioxide chemical fixationa

Scheme 2. Synthesized route of Mo@SBA-15

参考文献 64

[1]	Jahandar Lashaki, M.; Khiavi, S.; Sayari, A. Chem. Soc. Rev. 2019, 48, 3320. doi: 10.1039/c8cs00877a pmid: 31149678
[2]	de Kleijne, K.; Hanssen, S. V.; van Dinteren, L.; Huijbregts, M. A. J.; van Zelm, R.; de Coninck, H. One Earth 2022, 5, 168.
[3]	Artz, J.; Muller, T. E.; Thenert, K.; Kleinekorte, J.; Meys, R.; Sternberg, A.; Bardow, A.; Leitner, W. Chem. Rev. 2018, 118, 434.
[4]	Zhang, J.; Wang, L.; Liu, S.; Li, Z. Angew. Chem., Int. Ed. 2022, 61, e202116982.
[5]	Meylan, F. D.; Moreau, V.; Erkman, S. J. CO₂ Util. 2015, 12, 101.
[6]	Buttner, H.; Longwitz, L.; Steinbauer, J.; Wulf, C.; Werner, T. Top. Curr. Chem. 2017, 375, 50.
[7]	Schaffner, B.; Schaffner, F.; Verevkin, S. P.; Borner, A. Chem. Rev. 2010, 110, 4554.
[8]	Taherimehr, M.; Serta, J. P.; Kleij, A. W.; Whiteoak, C. J.; Pescarmona, P. P. ChemSusChem 2015, 8, 1034. doi: 10.1002/cssc.201403323 pmid: 25688870
[9]	Guo, L.; Lamb, K. J.; North, M. Green Chem. 2021, 23, 77.
[10]	Kotanen, S.; Wirtanen, T.; Mahlberg, R.; Anghelescu-Hakala, A.; Harjunalanen, T.; Willberg-Keyrilainen, P.; Laaksonen, T.; Sarlin, E. J. Appl. Polym. Sci. 2023, 140, e53964.
[11]	Zhang, X.; Zhao, B.; Fu, S.; Seruya, R. S.; Madey III, J. F.; Bukhryakova, E.; Zhang, F. Macromolecules 2024, 57, 2858.
[12]	Giri, P.; Barath V, S.; Dhurua, S.; Maity, S.; Gazi, R.; Jana, M. Phys. Chem. Chem. Phys. 2024, 26, 9317.
[13]	Rehman, A.; Saleem, F.; Javed, F.; Ikhlaq, A.; Ahmad, S. W.; Harvey, A. J. Environ. Chem. Eng. 2021, 9, 105113.
[14]	Qin, Y.; Guo, H.; Sheng, X.; Wang, X.; Wang, F. Green Chem. 2015, 17, 2853.
[15]	Jiang, X.; Gou, F.; Fu, X.; Jing, H. J. CO₂ Util. 2016, 16, 264.
[16]	Maeda, C.; Taniguchi, T.; Ogawa, K.; Ema, T. Angew. Chem., Int. Ed. 2015, 54, 134.
[17]	Chaugule, A. A.; Tamboli, A. H.; Kim, H. Fuel 2017, 200, 316.
[18]	Wang, B.; Cao, X.; Wang, L.; Meng, X.; Wang, Y.; Sun, W. Inorg. Chem. 2024, 63, 9156.
[19]	Xiao, L.-F.; Li, F.-W.; Xia, C.-G. Appl. Catal., A 2005, 279, 125.
[20]	Vyskočilová, E.; Šafařík, D.; Zítová, K.; Vrbková, E.; Dimitrov, R.; Vagenknechtová, A.; Červený, L. Catal. Lett. 2022, 152, 3576.
[21]	Pappuru, S.; Shpasser, D.; Carmieli, R.; Shekhter, P.; Jentoft, F. C.; Gazit, O. M. ACS Omega 2022, 7, 24656.
[22]	Mikšovsky, P.; Rauchenwald, K.; Naghdi, S.; Rabl, H.; Eder, D.; Konegger, T.; Bica-Schröder, K. ACS Sustainable Chem. Eng. 2024, 12, 1455.
[23]	Campisciano, V.; Gruttadauria, M.; Giacalone, F. ChemCatChem 2018, 11, 90.
[24]	Jayakumar, S.; Li, H.; Chen, J.; Yang, Q. ACS Appl. Mater. Interfaces 2018, 10, 2546.
[25]	Liu, L.-H.; Liu, L.; Chi, H.-R.; Li, C.-N.; Han, Z.-B. Chem. Commun. 2022, 58, 6417.
[26]	Helal, A.; Zahir, M. H.; Albadrani, A.; Ekhwan, M. M. Catal. Lett. 2023, 153, 2883.
[27]	Helal, A.; Alahmari, F.; Usman, M.; Yamani, Z. H. J. Environ. Chem. Eng. 2022, 10, 108061.
[28]	Qiu, L.-Q.; Li, H.-R.; He, L.-N. Acc. Chem. Res. 2023, 56, 2225.
[29]	Wang, K.; Li, H.; Yang, L.; Luo, Y.-Z.; Yao, Z.-J. Surf. Interfaces 2024, 45, 103845.
[30]	Li, J.; Han, Y.; Lin, H.; Wu, N.; Li, Q.; Jiang, J.; Zhu, J. ACS Appl. Mater. Interfaces 2020, 12, 609.
[31]	Xu, L.; Wang, Y.; Sun, Z.; Chen, Z.; Zhao, G.; Kühn, F. E.; Jia, W.-G.; Yun, R.; Zhong, R. Inorg. Chem. 2024, 63, 1828.
[32]	Pourhassan, F.; Khalifeh, R.; Eshghi, H. Fuel 2021, 287, 119567.
[33]	Zhao, D.; Feng, J.; Huo, Q.; Melosh, N.; Fredrickson, G. H.; Chmelka, B. F.; Stucky, G. D. Science 1998, 279, 548. doi: 10.1126/science.279.5350.548 pmid: 9438845
[34]	Yang, P.; Zhao, D.; Margolese, D. I.; Chmelka, B. F.; Stucky, G. D. Nature 1998, 396, 152.
[35]	Dokhaee, Z.; Ghiaci, M.; Farrokhpour, H.; Buntkowsky, G.; Breitzke, H. Ind. Eng. Chem. Res. 2020, 59, 12632.
[36]	Liu, Y.; Hu, Y. H.; Zhang, J. R.; Zhou, J. S.; Zhang, Z. K.; Wang, L.; Zhang, J.-L. Microporous Mesoporous Mater. 2022, 337, 111873.
[37]	Pickens, R. N.; Neyhouse, B. J.; Reed, D. T.; Ashton, S. T.; White, J. K. Inorg. Chem. 2018, 57, 11616.
[38]	Shi, Z.; Su, Q.; Ying, T.; Tan, X.; Deng, L.; Dong, L.; Cheng, W. J. CO2 Util. 2020, 39, 101162.
[39]	Sankar, M.; Ajithkumar, T. G.; Sankar, G.; Manikandan, P. Catal. Commun. 2015, 59, 201.
[40]	Yuan, C.; Huang, Z.; Chen, J. Catal. Commun. 2012, 24, 56.
[41]	Cang, R.; Lu, B.; Li, X.; Niu, R.; Zhao, J.; Cai, Q. Chem. Eng. Sci. 2015, 137, 268.
[42]	Mohammadi Ziarani, G.; Ebrahimi, Z.; Mohajer, F.; Badiei, A. Res. Chem. Intermed. 2021, 47, 4583.
[43]	Wang, D.; Guo, X.-Q.; Wang, C.-X.; Wang, Y.-N.; Zhong, R.; Zhu, X.-H.; Cai, L.-H.; Gao, Z.-W.; Hou, X.-F. Adv. Synth. Catal. 2013, 355, 1117.
[44]	Zhou, L.; Peng, L.; Ji, J.; Ma, W.; Hu, J.; Wu, Y.; Geng, J.; Hu, X. J. CO₂ Util. 2022, 58, 101910.
[45]	Leofanti, G.; Padovan, M.; Tozzola, G.; Venturelli, B. Catal. Today 1998, 41, 207.
[46]	Roshan, K. R.; Kathalikkattil, A. C.; Tharun, J.; Kim, D. W.; Won, Y. S.; Park, D. W. Dalton Trans. 2014, 43, 2023.
[47]	Kathalikkattil, A. C.; Kim, D.-W.; Tharun, J.; Soek, H.-G.; Roshan, R.; Park, D.-W. Green Chem. 2014, 16, 1607.
[48]	Xie, Y.; Zhang, Z.; Jiang, T.; He, J.; Han, B.; Wu, T.; Ding, K. Angew. Chem., Int. Ed. 2007, 46, 7255.
[49]	Chen, F.; Tao, S.; Liu, N.; Dai, B. Polyhedron 2021, 196, 114990.
[50]	Li, C.; Xiong, W.; Zhao, T.; Liu, F.; Cai, H.; Chen, P.; Hu, X. Appl. Catal., B 2023, 324, 122217.
[51]	Ratzenhofer, M.; Kisch, H. Angew. Chem., Int. Edit. 1980, 19, 317.
[52]	Tenhumberg, N.; Büttner, H.; Schäffner, B.; Kruse, D.; Blumenstein, M.; Werner, T. Green Chem. 2016, 18, 3775.
[53]	Chen, J.-H.; Deng, C.-H.; Fang, S.; Ma, J.-G.; Cheng, P. Green Chem. 2018, 20, 989.
[54]	Kim, Y.; Ryu, S.; Cho, W.; Kim, M.; Park, M. H.; Kim, Y. Inorg. Chem. 2019, 58, 5922.
[55]	Li, J. W.; Tao, S.; Chen, F.; Li, M.; Liu, N. J. CO₂ Util. 2023, 69, 102384.
[56]	Yu, W.-D.; Zhang, Y.; Han, Y.-Y.; Li, B.; Shao, S.; Zhang, L.-P.; Xie, H.-K.; Yan, J. Inorg. Chem. 2021, 60, 3980.
[57]	Shi, Z.; Niu, G.; Han, Q.; Shi, X.; Li, M. Mol. Catal. 2018, 461, 10.
[58]	Cheng, W.; Chen, X.; Sun, J.; Wang, J.; Zhang, S. Catal. Today 2013, 200, 117.
[59]	Rios Yepes, Y.; Quintero, C.; Osorio Meléndez, D.; Daniliuc, C. G.; Martínez, J.; Rojas, R. S. Organometallics 2019, 38, 469.
[60]	Desens, W.; Werner, T. Adv. Synth. Catal. 2016, 358, 622.
[61]	Liu, J.; Yang, G.; Liu, Y.; Zhang, D.; Hu, X.; Zhang, Z. Green Chem. 2020, 22, 4509.
[62]	Motokucho, S.; Morikawa, H. Chem. Commun. 2020, 56, 10678.
[63]	Li, Y.-D.; Cui, D.-X.; Zhu, J.-C.; Huang, P.; Tian, Z.; Jia, Y.-Y.; Wang, P.-A. Green Chem. 2019, 21, 5231.
[64]	Sopeña, S.; Martin, E.; Escudero-Adán, E. C.; Kleij, A. W. ACS Catal. 2017, 7, 3532.